Document Detail

Structure Elucidation of the Diagnostic Product Ion at m/z 97 Derived from Androst-4-en-3-One-Based Steroids by ESI-CID and IRMPD Spectroscopy.
MedLine Citation:
PMID:  22173925     Owner:  NLM     Status:  Publisher    
Structure elucidation of steroids by mass spectrometry has been of great importance to various analytical arenas and numerous studies were conducted to provide evidence for the composition and origin of (tandem) mass spectrometry-derived product ions used to characterize and identify steroidal substances. The common product ion at m/z 97 generated from androst-4-ene-3-one analogs has been subject of various studies, including stable isotope-labeling and (high resolution/high accuracy) tandem mass spectrometry, but its gas-phase structure has never been confirmed. Using high resolution/high accuracy mass spectrometry and low resolution tandem mass spectrometry, density functional theory (DFT) calculation, and infrared multiple photon dissociation (IRMPD) spectroscopy employing a free electron laser, the structure of m/z 97 derived from testosterone was assigned to protonated 3-methyl-2-cyclopenten-1-one. This ion was identified in a set of six cyclic C(6)H(9)O(+) isomers as computed at the B3LYP/6-311++G(2d,2p) level of theory (protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one and 2-cyclohexen-1-one). Product ions of m/z 97 obtained from MS(2) and MS(3) experiments of protonated 3-methyl-2-cyclopenten-1-one, 2-methyl-2-cyclopenten-1-one, 2-cyclohexen-1-one, and testosterone corroborated the suggested gas-phase ion structure, which was eventually substantiated by IRMPD spectroscopy yielding a spectrum that convincingly matched the predicted counterpart. Finally, the dissociation pathway of the protonated molecule of testosterone to m/z 97 was revisited and an alternative pathway was suggested that considers the exclusion of C-10 along with the inclusion of C-5, which was experimentally demonstrated with stable isotope labeling.
Mario Thevis; Simon Beuck; Sebastian Höppner; Andreas Thomas; Joseph Held; Mathias Schäfer; Jos Oomens; Wilhelm Schänzer
Related Documents :
21983815 - Chiral analysis of amphetamines, methadone and metabolites in biological samples by ele...
21798545 - A test to determine the nature and presence of the memory effect columns packed with th...
21222145 - Resonance rayleigh scattering, second-order scattering and frequency doubling scatterin...
21601835 - A new method for the quantification of chitin and chitosan in edible mushrooms.
22265515 - Preconcentration via ion associated complexes combined with inductively coupled plasma ...
18646865 - Using liposomal fluorescent biolabels to develop an immunoaffinity chromatographic bios...
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2011-12-16
Journal Detail:
Title:  Journal of the American Society for Mass Spectrometry     Volume:  -     ISSN:  1879-1123     ISO Abbreviation:  -     Publication Date:  2011 Dec 
Date Detail:
Created Date:  2011-12-16     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9010412     Medline TA:  J Am Soc Mass Spectrom     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Institute of Biochemistry-Center for Preventive Doping Research, German Sport University Cologne, Am Sportpark Müngersdorf 6, 50933, Cologne, Germany,
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine

Previous Document:  Uterine Artery Embolization for Uterine Leiomyoma: Role of Uterine Artery Doppler in the Pre-Interve...
Next Document:  Open-Shell Complexes Containing Metal-Germanium Triple Bonds.